Process of producing fast dyeings



Patented Feb. 27, 1940 UNITED STATES PATENT OFFICE PROCESS OF PRODUCING FAST DYEINGS v Friedrich Ebel, Mannheim, and Karl Koeberle,

Ludwigshafen-on-the-Rhine, Germany, assignors to General Aniline-& Film Corporation, a corporation of Delaware No Drawing. Application November 18,1937, Se-

rial No. 175,255. In Germany November 25,

4 Claims.

The present invention relates to a process of producing fast dyeings.

We have found that fast dyeings on materials consisting of or containing cellulose or regener- 5 ated cellulose are produced by treating the said materials with the solution of a diazo compound 1 having aflinity for the goods to be dyed and with the solution of a compound capable of coupling.

A diazo compound has aflinityfor the goods to be dyed if it has at least one of the following characteristics: A group consisting of three or more condensed nuclei; the grouping" -HN-CO-NH; two or more carboylamino groups; a group I R-N=N-R', RCH=CH-R' v R--N=CHR' wherein R and R'are aromatic radicals; a structure like diphenyl. Furthermore, the diazo compounds must be soluble, which is the case, for example, if the molecule contains at least one L aza nitrogen atom or a quaternary nitrogen atom,

or a polyglycolether, radical.

The following statement will further illustrate our invention. I

Generally speaking, compounds containing at least three condensed nuclei may be used for the purpose of the present process. The afflnity for the fiber increases by the adding on of further rings. For this purpose there may be employed especially aminobenzeneacridines', I aminopyri-- and dinopyrenes, amino tribenzophenazines similar higher cyclic compounds. Compounds 35 having several diazo groups may also be used,

as for example, tetrazotized diaminodiquinolinonaphthalene-orthe tetrazo compound of the following diamine:

. '01 1 Q HNHIK I n o \N NH: I

The molecule may also contain other solubiliz-- ing groups. For example, the compound (3H1 N.CHI.CH:.O.CH1.CHI.O.CHI-CHLOJJHLOH.0H

salt having 2-(4'-aminophenyl)-quinoline, 1-aza-9-chlor-2- (iaminophenyl) anthracene, l-aza aminophenyl) phenanthrene, '2.4-diamino 9 phenylacridine and other similar compounds.

The same efiect as the diphenyl linkage have also linkages between an aromatic ring and an azole ring, e. g. an oxazole, thia'zole, imidazole, or triazole ring. A simple compound of this kind is diazotized dehydrothiotoluidine. Higher compounds having even a better affinity for the fiber are, for example, the diazo compounds derived from the following amines:

- For rendering the amino compounds soluble, in-

stead of the aza nitrogen also one of the other an groups as stated above may be present. example is the compound having the following 6 constitutionz' stitution:

NHONH. co

'\NHONH| yields fairly strong dyeings.- Very powerful dyeings are also obtained by using compounds having several carboylamino groups, as for example gNE-O-NH-O OONH,

The amnity for the fiber is also increased by the 1 addition of higher radicals, as is the case in the following compounds:

'As a' changed carboylamino group there may 70 also be mentioned the following group:

diaminodiphenyl urea having the following con- 1 Examples for compounds of this kind are the following:

LN N

NHN

NzC] NgCl NaCl j as a 1 EN N/ NH The presence ofwater solubilizing groups, for example the presence of aza nitrogen atoms, is preferable;

Further groups, producing by their presence, ailinity for the fiber of diazo compounds, 'are the azo-, ethyleneand the azeomethine groups. The

double linkages of these groups must be in conjugation with aromatic nuclei. For producing satisfactorily powerful and fast dyeingsit isindicated to employ compounds which contain besides onerof the said groups other characteristics described above or also several groups of the kind 45 mentioned herein. For example, the following FO 'O compounds may be mentioned:

OCH: N I 5o I N=N-j-NH=v .50

ooamOnmoo-Omn-on on, I

N i snails-Own.

NB NB: oo I NE NH:

Geo-NH I I so The term "diazo compounds according to this invention means not only the .true diazonlum 05 salts, but also their double compounds with metal .halides, as for example with zinc chloride, tin chlorides, boron fluoride, and also antidiazotates, nitrosamines, diazos ulphonic acids, diazo-anhydrides, diazoamino compounds, provided they are water soluble either as such or in the-form of their salts, provided they have afllnity for the fibers and provided they are capable of reacting with compounds capable of coupling to form azo dyestuffs, whereby the saidreaction may be carried out either directly or in the presence of agents promoting coupling, such as acids, sodium acetate or carbonate, caustic soda solution, pyridine or light.

According to this invention all materials consisting wholly or partly of cellulose or regenerated cellulose may be dyed, as for example woven products from cotton, jute, hemp, flax, coir, viscose artificial silk, copper, artificial silk and de-acylated cellulose nitrate or acetate, and also films or other products from the said substances.

The, process is carried out by introducing the goods to be dyed at ordinary or slightly elevated temper ture into a solution of the diazo compound which may contain wetting agents and/or saltsto facilitate the completion of the absorption., After some time, usually at the most after an hour, the goods are removed from the bath,

sired, and then treated with a solution of a compound capable otcoupling. The coupling may be initiated by the agents enumerated above if neces-.

sary. The accelerating agents may also be allowed to act first, the compound capable of cou-' pling then being introduced. Similarly it is also possible to apply the diazo compound and the compound capable of coupling to the goods at the same time, the agents promoting coupling then being allowed to act subsequently.

Instead of using a single diazo compound or a single compound capable of coupling, two or more of such compounds may be used in admixture. Furthermore by allowing two or more compounds capable of coupling to act at different times and places, multicolor designs may be produced. For this purpose, for example, there may be printed onto the goods treated with the diazo compound a compound capable of coupling together with a thickening agent and an agent accelerating the coupling in the form of a pattern. The nonprinted parts are then developed in a solution of a second coupling compound. There may also be printed on the goods treated with the diazo compound patterns with one or more compounds capable of coupling together with thickening agents, the diazo compound then being removed from the non-printed parts by subsequent wash-.

ing. Single color and multicolor prints are thus obtained on a white ground.

The said method of dyeing is very simple and protects the goods dyed. All the processes take place in a short time at ordinary temperature in neutral or almost neutral solution. Materials which are especially sensitive, such as mixed fabrics of animal and vegetable fibers or of animal fibers and cellulose hydrate fibers, are therefore suitable for dyeing according to this invention. By reason of thelarge number of suitable compounds, a great variety of shades of color may be obtained. The fact that even rdyeings produced with the aid of compounds having water solubilizing groups have satisfactory fastness to moisture is of special importance. Dyeings without such groups have a specially good fastness to moisture. Therefore, it is possible to dye previously, according to the present invention. the portion of cellulose and/or of cellulose hydrate in'mixed fabrics of cellulose and/or cellulose hydrate fibers and then to dye subsequently the portion of other fibers with dyestuffs suitable for these fibers.

The dyeings obtainable according to the present process may be aftertreated in any desired manner: For example, diazotizable dyestufls may be diazotized on the fiber and reacted with a compound capable of coupling, and vice versa suitable dyestufis may be coupled on the fiber with diazo compounds, or dyestuffs capable of forming.

"formaldehyde, and still others with hypochlorites.

The following examples willfurther illustrate, how .our invention may be performed and carried out in practice. unless otherwise stated.

The parts are by weight,

The ratio of the parts by weight and the parts by volume is grams to cubic centimeters.

Example 1 1.22 parts of S-amino-7.8-benzeneacridine N NHr are dissolved in 50 parts by volume of water and.

2.25 parts by volume of 10 N hydrochloric acid; the amine is diazotized by the addition of 5 parts of N sodium nitrite solution. Then the diazo solution is diluted with 1160 parts by volume of 10 per cent common salt solution.

In this solution 50 parts of cotton are-treated at ordinary temperature for 1 hour, squeezed out well and then introduced into a solution at 25 C. of 1.25 parts of 1pheny1-3methylpyrazolone- NHQ orange-yellow dyeings are obtained.

Example 2 1.8 parts of diamino-diquinolinonaphthalene are dissolved in, 50 parts of water and 4.5 parts by volume of 10 N hydrochloric acid and the amine is diazotized by the addition of 10 parts by volume of N sodium nitrite solution. Then the sosmall amount of warm glacial acetic acid.

lution is diluted with 1750 parts by volume of water.

In this bath 70 parts of cotton are bottomed in the manner described in Example 1. For develop:

ing a solution of 2 parts of 1-(4'-sulphophenyl) 3-carboxy-pyrazolone-g5) and 40 parts by volume of 2.5 N sodium acetate solution in 2000 parts by volume of water may be used- A Thus, a very fast yellow dyeing is obtained. Instead of the diazo compound employed there may also be used the diamine of the formula Example 3 1%13 parts of the compound having the following constitution:

A I? N CH:

N.CH1.CH3.0.QHmCHz.O.CH:.CHz.O.CHQ.0Hz.OH

O NH: (obtainable from 2-bromo-4-aminoanthrapyrimidine and methylaminoethyltriglycol; brown crystals, melting point at from 328 to 329 C.) are dissolved in 20 parts of water and 1.25 parts by volume of 10 N hydrochloric acid and diazotized with 2.5 parts by volume of N sodium nitrite solution at from to C. Then 40 parts of cotton are bottomed at ordinary temperature for half an hour in the diazo solution diluted with 1100 parts by volume of per cent common salt solution. The fabric is then squeezed out and developed in a bath containing in 1000 parts by volume 1 part of beta-naphthol and 4 parts of sodium acetate. After the development the cotton showing a red coloration is rinsed well with lukewarm water.

Example 4 By condensing beta-naphthisatine and paminoacetophenone an amino carboxylic acid is obtained which after splitting off the carboxylic group gives an amine having the following constitution:

This amine forms yellow crystals which melt at from 217 to 219 C. I

1.35 parts of the said amine are dissolved in a Then 2 parts by volume of 10 N hydrochloric acid are added. The solution freezes thus forming a brownish yellow crystal pulp. A solution of 1.1 parts by volume of 5 N sodium nitrite solution is added thereto at from 10 to C. Then the miizture is stirred until all dark orange ingredients have passed into solution and diluted.

with 1350 parts by weight of water. In the diazo solution thus obtained 50 parts of cotton are bottomed at from to C. for 1' hour. The fabric is then shaken well and introduced for half an hour into a bath containing 1.25 parts of beta-naphthol and 5 parts of sodium acetate in 1250 parts by volume. The cotton gets a powerful red, coloration. It is rinsed well and soaped while lukewarm. If other developers are employed instead of beta-naphthol other shades are obtained. For example, with 1-phenyl-3-methylpyrazolone-(5) a powerful orange yellow shade is obtained.

Similar results are obtained with the diazo compounds of the following amines:

(Prepared from l-chlor-2(N).3-naphthisatine and p-aminoacatophenone) COOCH:

(Esterification of the above compound; brown-yellow crystals melting point at from 228 to 230, 0.)

(Obtainable from 1-ch1or-2(N).3-naphthisatlne and pmminoacetophanone, then decarboxylated; yellow crystals, melting point at from 218 to 220 0.)

Furthermore there may be employed the amines of 2- (4'-aminophenyl) -quinoline, 2- (4-aminophenyl) -quinoline-4-carboxylic acid methyl ester,

- 9-(4"-aminophenyl) -phenanthridine, 4.4-diaminodiazaterphenyl,

(Prepared from 4-amlno-omega-chloracetophenone and ammonia; colorless crystals, melting point at from 187 to 189 C.)

' I dr'ochloric acid and diazotizedat from to C. with 1 part by volume of 5 N sodium nitrite Shade of A gent promoting Developer dyeing the coupling Z-naphthol Red Caustic soda soluon. 2-ethylaminonaphthalene "do": Sodium acetate. 1.3-diaminobenzene Sodium carbonate. 1.3-dismino-4-chlorbenzene. Do. 1.3-dibydroxybenzene do Caustic soda soluon. l-methyl-2.4-diaminobenzene do Sodium carbonate.

Phenol Yellow Caustic soda solu- 1 7 tion. l-ethylaminonaphthalene Red-brown... Sodium acetate.

2 ammonaphthalene 5 sul- Yellow-brown- Do.

phonic acid.

2 aminonaphthalene 6 suldo Do.

phonic acid.

1 henzoylamino 8 hydroxy- Violet Sodium carbonate.

naphthalene 4.6 disul- I phonic acid.

i-phenylaminonaphthalene-8- Violet-brown. Sodium acetate.

sulphonic acid.

2 amino S-hydroxynaphtha Brown. I Do.

leneo-sulphonic acid. Y

2'1? hydroxynaphthoylani- Red Sodium hydroxide.

2.3-hydroxynaphthoyl-betado Do. naphthylamine. (DiacetoacetyD-B.3-to1idid Yellow Do.

' .amarav or the amine of 2.7-dimethyl-9-(4'-aminophenyD-acridine Example 5 solution. The diazo solution is diluted with 1000 'parts by volume of 10 per cent common salt acetylamino-fi-hydroxynaphthalene- '7 -sulphonic acid sodium and 4 parts of sodium acetate in 1000 parts by volume. After half an hour, the artificial silk having a. powerful red coloration is removed from the development bath, rinsed with lukewarm water and soaped for a quarter of an hour at 40 C. with a solution of 5 grams of Marseille soap in a liter of water.

Instead of chloracetylaminohydroxynaphthalene sulphonic acid other compounds capable of coupling may be employed. The following list describes a number of dyeings thus obtainable:

Corresponding results are obtained by using the diazo-compounds of the following amines:

7.8-(4'- aminophenyltrlazolo) 4 azaphenan threne 7 5.6 (4'- -aminophenyltriazoloi -quinoline NHe. 9.10-(4'aminophenylthiazolo) 4 azaphenanthrene l r N s cONm (Prepared by converting lfl-amino-i-azaphenanthrene in known manner into l0-amino-9-metcapto-i-azaphenanthrene and then into 9.10-(4-nitrophenylthiazolo)-4-azaphenanthrene and reduction; yellow crystals, melting point 264 0.)

1-methyl-4.5-(4' aminophenylthiazolo) benzene. r

- Example 6 9.10-(4'-aminophenyltriazolo) 4 4 azaphenanthrene changes while treating with dimethylsulphate in hot anhydrous nitrobenzene into aquaternary ammonium compound probably having the following constitution:

Inc--41 3.0.86. NGNHs the reduction a diamine probably having the following tormula (white microcrystalline powder,- melting point 360.C.). In order to be able to diazotize this compound it is dissolved in cold concentrated sulphuric acid and precipitated again by pouring into ice water. Then the compound is freed from sulphuric acid. andsusnended in water without drying previously. An amount corresponding to 2.4 parts of the said compound in the form of this suspension isthen made up with water to form 50 parts by volume, 3 parts by volume of 10 N hydrochlorio acid are added and the whole diazotized at between 10 and 15 by the addition of 2 parts by volume of 5 N sodium nitrite solution. After a quarter of an hour the whole has passed into solution. It is then diluted with' water to form a total of 2400 parts by volume.

In the diazo solution thus prepared regenerated cellulose is bottomed at from 20 to 25 C. for an hour, squeezed ofi and developed with the developer solution described in Example 1. Powerful orange-yellow dyeings are thus obtained.

If 4.4'- or 3.3'-diaminodiphenyl urea is employed instead of the described diamine, the dyeings thus obtainedare considerably weaker.

Powerful .dyeings are obtained with the higher 20 molecular 5.5'-diamino-8.8-diquinonyl urea:

(Pre ared from s-aminoquinoline with phosgene, nitration and re notion of the nitro compound; yellow crystals, melting point at from 237 to 239 0.)

giving on the fiber with beta-naphthol a violet shade.

Other amines of this kind are $0 /NH. 0 O-O-NEO OONH,

(obtainable by reaction oi o-aminoquinoline with pare-nitrobenzoyl chloride, reduction of the nitro group, second reaction with pare nltrobenzo 1 chloride and repeated reduction; colorless crystals, melting po t 312 0.)

e0 moonnGrmoo-O-ma 55 (Obtainable by reaction of qulnoline fl-carboxylic acid chloride with para-mtraniline, reduction of the nitro group, reaction of the amine obtained with parn-nitrobenzoyl chloride and repeated reduction; colorless needles; melting point 320 0.)

70 (Pre ared from Murine-haze henanthrene and pare-nitrobenzoylchforide and following reduction of the itr crystals, melting point at from 244 to 245 6.) 0 group By using these amines, clear powerful dyeings are obtained.

- Example 8 2 molecular proportions of S-aminoquinoline are dissolved in ten times its amount of glacial acetic acid and stirred at from 40 to 50 C. after the addition of l molecular proportion of eye)- nuric chloride for 1 hour. The whole passes into solution. "Then a yellow crystalline precipitate separates; it is filtered off by suction, washed with glacial acetic acid and water and dried. For the further reaction parts of this compound,

10 parts of para-nitroaniline, 5 parts of anhy- HNYNYNH 1.5? parts of this amine are dissolved in 45 parts by volume of methanol and 2 parts by volume of 10 N hydrochloric acid. After the addition of 50 parts of water the solution is diazotized with 1 part by volume of 5 N sodium nitrite solution which is added at from 10 to C. at once. Then the diazo solution is diluted with 1450 parts of water.

The dyeing process is carried out according to the prescriptions of the foregoing examples. Powerful and clear shades are obtained.

Instead of the aforesaid amine the amine having the following formula NH: NH:

may be employed. It is obtained if the action of the aminoquinoline and para-nitroaniline onto cyanuric chloride is reversed in consideration of the proportions to be changed.

1 the arc-(4' diazoniumphenyltriazolo) 4 aza- There may also be used the following compound obtainable from 2-'(4'-nitrophenyl)-4.6-dichlor- 1.3.5-triazine by reaction with 8-aminoquinoline and following reduction.

Example 9 In the usual manner from diazotized G-aminoquinoline by coupling with aminohydroquinonedimethyl ether a compound having the following constitution: OCH:

is obtained, the diazonium salt of which goes'on cellulose from aqueous solution and may then be developed. For example, beta-ethylnaphthylamine yields red dyeings.

Compounds having similar properties are as follows:

CH=CHONH| (Ohtainable from qulnoline-fi-aldehyde and p-nitrophenyl acetic acid and reduction of the nitro group) (obtainable from 4-nitro-4'-amino-azobenzene and benzoyl chloride and reduction of the nitro group) Example 10 phenanthrene-benzene sulphonate crystallizes in the form of yellow needles. The compound is then filtered off by suction, washed and dried at low temperature. It melts at 145 C. and is stable at ordinary temperature and in the dark at any time.

The benzene sulphonate is not soluble in water, but weakly soluble. in dilute cold hydrochloric acid.

10 parts of this benzene sulphonate and 7.5 parts by volume of 10 N hydrochloric acid are dissolved in 3000 parts of water. Then the acid is neutralized with 1 part of sodium acetate.

In this bath 120 parts of a fabric of per cent cellulose hydrate and. '70 per cent wool are treated at ordinary temperature for an hour. The fabric is squeezed and introduced at ordinary temperature into a bath consisting of:

3 parts of 2-isobutylaminonaphthalene-l-sulphonic acid sodium, 12 parts of sodium acetate, 1.74 parts of anthosine BN (cf. Schultz-Julius, Farbstofitabellen, 7th edition, vol. 1, No. 51), 15' parts of sodium sulphate, 3000 parts of water and 3 parts by volume of 30 per cent acetic acid.

The dye-bath is heated to boiling within half an hour; this temperature is kept for half an hour. Then 3 parts by volume of 30 per cent acetic acid are added and the boiling is continued for half an hour. The dyed fabric is rinsed well with lukewarm water. A powerful red dyeing covering equally both kinds of fibers is thus obtained.

What we claim is:

1. A process of producing fast dyeings on cellulosic material which comprises treating the good to be dyed with the solution of a diazo compound having at least one aza nitrogen and at least three rings, and subsequently with a coupling component. I

2. A process of producing fast dyeings on vege-- table fibers which comprises treating the good to be dyed with the solution of a diazo compound having at least one aza nitrogen and at least three rings, and subsequently with a coupling component.

3. A process of producing fast dyeings on regenerated cellulose which comprises treating the good to be dyed with the solution of a diazo compound having at least one aza nitrogen and at least three rings, and subsequentlywith a coupling component.

4. A process of producing fast dyeings on mixtures of regenerated cellulose and animal fibers which comprises treating the good to be dyed with the solution of a diazo compound having at least one aza nitrogen and at least three rings, and subsequently with a coupling component.

FRIEDRICH EBEL, KARL KOEBERLE. 

